tditors


The Science and Technology
of
Carbon Nanotubes

The Science and Technology
of
Carbon Nanotubes
Edited
by
Kazuyoshi Tanaka
Kyoto University, Japan
Tokio Yamabe
Kyoto University, Japan
Kenichi Fukui
t
Institute
for
Fundamental Chemistry, Japan
'999
Elsevier
Amsterdam
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Oxford

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First edition 1999
Library of Congress Cataloging
in

in
the carbon cathode used for the arc-
discharging process preparing small carbon clusters named by fullerenes. The
structure of CNT consists of enrolled graphitic sheet,
in
a word, and can be
classified into either multi-walled or single-walled CNT (MWCNT or SWCNT)
depending on its preparation method. It is understood that CNT is the material
lying in-between fullerenes and graphite as a quite new member of carbon
allotropes.
It should be recognised that while fullerene has established its own field with a
big group of investigators, the raison d'&tre
of
the CNT should become, and
actually has become, more and more independent from that of fullerenes.
As
a
novel and potential carbon material, CNTs would be far more useful and
important compared with fullerenes from practical points of view
in
that they
will directly be related to an ample field of "nanotechnology". It seems that a
considerable number of researchers have been participating into the science of
CNTs and there has been remarkable progress in the both experimental and
theoretical investigations on MWCNT and SWCNT particularly during
the
last
couple
of
years. Moreover, almost at the same time, an obvious turning point

The newest magnetic, optical
and electrical solid-state properties providing vital base to actual application
technologies are described in Chaps.
8-
10.
Explosive research trends toward
application of CNTs including the prospect for large-scale synthesis are
introduced
in
Chaps.
11-14.
It is the most remarkable feature of this monograph
that it devotes more than a half of the whole volume (Chaps.
8-14)
to such
practical aspects. The editors truly appreciate that all of the authors should like
to offer the readers the newest developments of the science and technological
aspects
of
CNTs.
vi
It
is
our
biggest sorrow that
in
the course
of
preparation of this monograph one
of the Editors, Professor Kenichi Fukui, Nobel Laureate of 198

ed.
M.
Endo,
S.
Iijima and
M.
S.
Dresselhaus,
Pergamon,
Oxford,
1996.
vii
CONTENTS
Editorial
K.
Tanaka (Chief Editor)

111

Chapter
1
Prospect
late
K.
Fukui

1
Chapter
2
Synthesis and Purification of Multi-

Single-Walled
Carbon Nanotubes
K.
Tanaka,
M.
Okada and Y. Huang

40
Chapter
6
Phonon Structure and Raman Effect of
Single-Walled Carbon Nanotubes
R.
Saito,
G.
Dresselhaus and M.
S.
Dresselhaus

51
Chapter
7
Behaviour of Single-Walled Carbon
Nanotubes

in Magnetic Fields
H. Ajiki and
T.
Ando


Carbon Nanotubes
J.
-P. Issi and
J.
-C.
Charlier

107
Chapter
11
Capillarity in Carbon Nanotubes
D.
Ugarte,
T. Stockli, J M. Bonard,
A.
Chatelain and
W.
A.
de Heer
128
Chapter
12
Large-Scale Synthesis
of
Carbon
Nanotubes by Pyrolysis
K.
Tanaka, M. Endo,
K.
Takeuchi,

and T. Yamabe

164
Subject Index

184
Author Index

190
1
CHAPTER
1
Prospect
late
KENICHI
FUKUI
Institute
for
Fundamental Chemistry
34-4 Nishihiraki-cho, Takuno, Sakyo-ku
Kyoto
406-8103, Japan
Various mesoscopic systems have their own unique characteristics, some
of
which are of importance due to bridging function over classical and quantum
mechanics. It is quite natural that human beings living in macroscopic world
could hardly grasp the phenomena occurring in the microscopic world
in
an
intuitive manner. This situation offers a vital sense

In a mesoscopic system
in
which both classical- and quantum-mechanical
pictures become compatible even for a short time is realised, its pragmatic
significance would be very large considering technical level of today. This book
is expected to offer the starting point
of
such new developments. In
this
sense, I
like to express my wholehearted admiration
to
the eminent work
of
Dr.
Sumio
Iijima who first discovered CNT. The timely contents of this book are readily
conceivable by the excellent authors and
I
also appreciate the wisdom
of
my
colleague editors.
References
1.
2.
Zurek, W.
H.,
Physics Today,
1991,

Higashi, Tsukuba, Ibaraki
305-8565,
Japan
1
Introduction
Since the discovery of carbon nanotube
(CNT)
by Iijima
[
11, many researchers
have been attracted to this material and a large number of studies have been piled
up.
CNT
was first synthesized as a by-product in arc-discharge method
in
synthesis of fullerenes and are currently being prepared by many kinds of
methods including arc-discharge [2-141, laser ablation
[
15-20] and catalytic
decomposition of hydrocarbon
[2
1-27]. In addition, electrolysis [28] and solar-
energy E291 methods have also been proposed.
As
for the application of
CNT,
there has been a remarkable progress in recent days such as that to the field-
electron emitter [30-341, for instance. Considering such rapid growth in many
directions, we can expect that
CNT

pm. On the other hand,
SWCNT
is much thinner with the diameters from
1.0
to 1.4 nm.
There have been a considerable efforts at synthesis and purification
of
MWCNT
for the measurements of its physical properties. The time is, however, gradually
maturing toward its industrial application.
As
to
SWCNT,
it could not be
efficiently obtained at first and, furthermore, both of
its
purification and physical-
properties measurement were difficult. In 1996, it became that
SWCNT
could
be
efficiently synthesized
[
14,163 and, since then,
it
has become widely studied
mainly
from
the scicntific viewpoints.
In

form of a sharp tip with nanometer-scale radius of curvature, high mechanical
stiffness, chemical inertness and high electrical conductivity.
In
addition to these
eminent characteristics it also has the unique coaxial shape, which will afford
good possibilities to
be
applied to various fields of industry (see Chaps.
13
and
14).
2.
I
Synthesis
2.1.1 Electric arc discharge
When the arc-discharge is carried on keeping the gap between the carbon
electrodes about
1
mm, cylindrical deposit forms on the surface of the cathode.
Diameter
of
this cathode deposit
is
the same as that of the anode stick. Under the
conditions that diameter of the anode carbon is
8
mm with the arc-electric current
of
80
A

500
Torr. When this value becomes below
100
Torr, almost no MWCNT grow. This
contrasts to that the highest quantity of fullerene
is
obtained when the pressure
becomes
100
Torr
or
less.
Another important parameter is the electric current for discharge.
If
the current
density is too high, the quantity of the hard shell increases and that of the
MWCNT decreases.
To
keep the arc discharge stable and the electrode cool are
effective to increase
in
the product quantity of MWCNT.
A
considerable quantity
of graphite is produced
in
the cathode deposit even under the most suitable
condition to the synthesis of MWCNT.
The bundle
of

mass
production possible.
Fig.
2. STM image of MWCNT [6b].
2.1.2 Laser ablation
Laser-ablation method shown in Fig.
3
was
usee.
when C6o was first discovered
in
1985
[15].
This method has also been applied for the synthesis of CNT, but
length of MWCNT is much shorter than that by arc-discharge method
[
171.
Therefore, this method does not seem adequate to the synthesis of MWCNT.
However,
in
the synthesis of SWCNT described later (Sec.
3.1.2),
marvelously
high yield has been obtained by this method. Hence, laser-ablation method has
become another important technology
in
this respect.
2.1.3
Catalytic decomposition of hydrocarbon
For extension of the application of MWCNT, the key technology is obviously

of
the
laser-ablation method.
Furnace
Cat
al
yst
I
I
oas
flO+
Fig.
4.
Schematic drawing of the apparatus used for the catalytic decomposition
of
hydrocarbon.
MWCNT synthesized by catalytic decomposition
of
hydrocarbon does not
contain nanoparticle nor amorphous carbon and hence this method is suitable for
mass production. The shape of MWCNT thus produced, however,
is
not straight
more often than that synthesized by arc-discharge method.
This
difference could
be ascribed to the structure without pentagons nor heptagons
in
graphene sheet
of

700
Acetylene
22,23
Zeolite
or
Clay support Ion exchange
700
Acetylene
22
Graphite support Impregnation
700
Acetylene
23
Ultra fine particle Decomposition of
800
Acetylene
24
Silica support Sol-gel process
700
Acetylene
25
Co Ultra fine particle Laser etching of Co
1000
Triazine
26
Ultra
fine
particle Decomposition
of
800

800
Acetylene
24
W
Ultra fine particle Decomposition of
800
Acetylene
24
metal carbonyl
thin film
metal carbonyl
Ni(C8H
1212
Mo*
metal carbonyl
metal carbonyl
'MO*=(NH~)~~+~[MO~
~~(N0)~40~20(OH)~~(H2~)~olo3~OH~0.
2.2
Purification
2.2.1
Isolation of MWCNT
In the isolation process of MWCNT, nanoparticles and graphite pieces should
be
first removed. It is considerably difficult, indeed, to execute the isolation of
MWCNT. The main reason
for
this comes from that the usual separation
methods, such
as

In order to accelerate the oxidation rate
of
graphite at lower temperature and to
7
increase the crop quantity after burning, the raw cathode sediment is treated with
CuC12 to give the graphite-Cu compound prior to the burning process
[38].
This
compound can be burnt at lower temperature and hence undesirable consumption
of
MWCNT is avoided.
Fig.
5.
Scanning electron microscope (SEM) images
of
aligned MWCNT
of
uniform
length
(40
pm) and diameters
(30-SO
nm).
Scales bars are
10
pm
(top) and
1
pm
(bottom) (Courtesy

7
shows a typical
transmission electron microscope (TEM) picture of MWCNT with an open end,
which reveals that a cap is etched off and the central cavity is exposed.
Fig.
7.
TEM
image
of
SWCNT
growing radially from
a
La-carbide particles
[lob].
3
SWCNT
Preparation research of SWCNT was also put forth by Iijima and his co-worker
[3]. The structure of SWCNT consists of an enrolled graphene to form a tube
without seam. The length and diameter depend on the kinds of the metal catalyst
used in the synthesis. The maximum length is several pm and the diameter
varies from
1
to 3 nm. The thinnest diameter is about the same as that of C6o
(i.e., ca.
0.7
nm). The structure and characteristics of SWCNT are apparently
different from those of MWCNT and rather near to fullerenes. Hence novel
physical properties of SWCNT as the one-dimensional material between
molecule and bulk are expected. On the other hand, the physical property of
MWCNT is almost similar to that of graphite used as bulk [6c].

Low
co
Fullerene soot
LOW
Tube soot High
Weblike High
/compounds conditions'
swcNT2
swcNT3
FeN Fullerene soot Very high
Tube soot Very high
Webli ke Very high
Fe/Co Fullerene soot
LOW
Tube
Soot High
Weblike Very high
Ni/Co Fullerene soot Very high
Tube soot Very high
Weblike Very
high
Ni/Cu Tube soot
Low
Ni/Ti Tube soot Very low
cu/co Tube soot
LOW
Y
20&0
Tube soot Low, radial
YC2

[3],
Co
[4],
Ni
[8,
IO]
or
rare-earth element
[IO]
was employed
as
the catalyst
(see
Fig.
7).
In these syntheses, however, the
yield
of
SWCNT was quite low. In the improved method, the catalyst consisting
of
more than one element such as Co-Pt
[
12,131
or
Ni-Y
[
141
is used to increase
the yield
of

1401.
3.1.3 Catalytic synthesis
Very recently, it has been reported that SWCNT can be synthesized by
decomposition of benzene with Fe catalyst
1271.
It would be of most importance
to establish the controllability of the diameter and the helical pitch in this kind
of synthesis of SWCNT toward the development
of
novel kinds
of
electronic
devices such as single molecule transistor 1411. It can be said that this field is
full of dream.
3.2
Purrj2ation
Since SWCNT is easily oxidised compared with MWCNT [42], the purification
process such as the burning method cannot
be
applied to that purpose. Tohji
et
al., however, have succeeded
in
this
by employing the water-heating treatment
[43] and, furthermore, the centrifuge [44] and micro-filtration
[39,
441 methods
can also be employed. It has recently been reported that SWCNT could be
purified by size-exclusion chromatography method

or
Ni plays
the important role and their combination or addition of the third element such as
Y
produces SWCNT
in
an efficient manner. But
it
is
still difficult in the laser-
ablation method to produce gram quantity of SWCNT. Nonetheless, remarkable
progress
in
the research of physical properties has been achieved in thus
synthesized SWCNT.
Fe, Co
or
Ni is also crucial
in
the catalytic decomposition of hydrocarbon.
In
order to efficiently obtain CNT and to control its shape,
it
is necessary and
indispensable
io
have enough information
on
chemical interaction between
carbon and these metals.

CNT
commenced in Japan and, nowadays, a large number of
investigators
from
all over the world participate in the research. It
is
considercd
that it is now high time for the turning point in the study on
CNT
in the sense
that the phase
of
research should shift from basic to applied
science
including
more improvement
in
efficiency
of
the synthesis, separation and purification.
It
is
expected that
CNT
will be one of the most important materials in the 21st
century and, hence, it
is
the most exciting thing for
us
to participate

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14
CHAPTER
3
Electron Diffraction and Microscopy of
Carbon Nanotubes
SEVERIN AMELINCKX,]
AMAND
LUCAS2
and

to
the literature
[
1-61.
2
Observations
2.1 Electron diffraction
(ED)
patterns
[7,8]
A
diffraction pattern of a single MWCNT (Fig.
1)
contains in general two types
of reflexions (i) a row
of
sharp
00.1
(1
=
even) reflexions perpendicular to the
direction
of
the
tube
axis, (ii) graphite-like reflexions of the type ho.0 (and hh.0)
which are situated
in
most cases
on